Noncatalytic alkylation under high pressure



Aug. 15, 1950 F. R. RUSSELL ,5

NONCATAL Y TIC ALKYLATION UNDER'HIGH PRESSURE Filed m. 4, 1946 FEED M mTuiLE.

Coupnassom Francis Q. ussezz Sam/enter I BSMQLDOPYZQES tions toproduce parafllni'c products 1 perature the shorter the contact time. "I'h,e ;p13pd=-.o

Patented Aug. 15, 950

UNITED PATENT OFFICE M V NON MALY'HC ALKYLATION UNDER a 1 ranssoma Francis R, Russell, Scotch lPlains, N. 3., assiggnor to Standard Qil Development gCompany, a corporation of Delaware Application -Dec ember4, 1946, Serial No. 713,897

51 This invention relates to a, process for con: verting hydrocarbons oft-higher molecular weight and relates more particularly to a process ferreacting parafiins and olefins to. produce higher molecular weight products suitable as Diesel fuel, jet-fuel, etc. 7. It is known to react paraffins with olefins unmrsssui e. n. t e absence '9; catal sts l duceantiknock 'inotor fuels. Since axnixtur'gi c .Ql r d t arx he t oce olefins "to paraffins can be increased and olefin po ml i ifi fiifillc ii 'l high Pressures above 30,000 lbs. are used. When such extremely high pressures are used, thegreaction will take place un er crewball. owe n: en u It has ne een 3 .1

20 mam/is e The reaction is particularly well suited tothe conversion ofilga's'eonsisoparafiinsi together with any of the gaseous olefins into :liquid hydrocar as s ta le .P ese .iuels. le ree s.

like.

and allowing the rni gtur e to temp tures of at least 300 B. The time 0 contact depends. ripen thetemperature. the higher the. items ucts are cooled and normally liquid hydrocarbons are separated by fractionation.

The products obtained are highly parafiinic, boil in the heavy naphtha or safety fuel range, but are low in octane number and are particularly suitable for use as jet fuels, Diesel fuels or @Qlaima rel-6 .34

iiuel oil. The reaction apparently continues with sewea sa tw ter; if. the ellsy et sia eceu sjiderably more olefin is used than para-inn, fl-he produ t ve low lirqmia numb rs imita e h the excess olefin is alky-lated rather than" polymerized.

The reaction proceeds without the use of-"caxtal ts. bu e edii en o a sm 9.ne c arche .Q li b n rr qsi i ben ii ia For fu ther nnr s ie f t e i ren iee eten may helme 1 Qmne -QF P'in m-T Referring now to this drawing a mixture m at ss are isse taee 1 a 'n e abo t 9 cem n Q p epx eu leiwduee by l n d. tore sse l6 elem 1 00,

The .product.

. D hg y hea a relatively low pressure by reducing yalve $9, c esiuqt heur sses thrq ehzc e rm a d; fractiona reactor. Bottoms from the fractionator are passed through line M to storage tank I5.

A number of runs have been carried out on the alkylation of isoblitane with propylene with and without the use of benzoyl peroxide as a promoter. according to the above-described procedss reader b l ne. i8 t. a c 9 $15 090; lbs. p r senate u i nedu iuer ce 48 and fi lly to QV h edfi mtheitra-ctionator 1 is ondensed rsc szl clithmuehli e breathe ure. The results obtained illustrate the advantages of this invention and are tabulated below:

ture of said hydrocarbons containing about 30 mol percent of olefins to a temperature above 300 Reaction of propylene isob utane at extreme pressures Feed, mol Per Cent CaHu 29. 9 30. 7 30. 7 32.0 32.0 32.0 32.

Promoter None 0.1% Benzoyl Peroxide Pressure (atmJ 8500 Approx. Temp. F 550 550 380 350 550 550 640 Time, mins 90 92 92 90 5+ 5+ Recovery, Weight Per Cen 89 104 93 97 98 98 98 Conversion: Y 1

Per Cent CzHt. '69. 6 31.4 17. 1 34. 2 81.4 56.3 87. 9 Per Cent of iso' C4Hm 25. 8 13. 0 12. 7 12. 3 24. 0 13. 7 26.8 Yields, Weight Per Cent on Charge:

C to E.P 12.6 9.6 5.9 9.7 23.5 15.2 24.0 400 390 324 370 400 382 400 16. 6 8.0 7. 8 V 8. 1 14. 0 9. 3 18. 2

o Bromide No.:

C to E. P., ave l1. 9 4. 5 0.8 0. 7 5. 7 6.0 13.4 C5 to E. P., Max. 29.2 21. 4 1.0 2.0 34. 7 14. 9 51. 7 Bottoms, ave 4. 1

Cut #13 Btms. 6+7+8 Btms. A. P. I 41.7 35-4 43.3 42.2 45.0 36.8 44.1 -RT 1.4494 1. 4671 1. 4464 1.4498 1.4459 1.4643 1.4464 Anil. Pt., F 129 198 130 186 134 Approx. Mid B. P., F 376 400+ 360 I 380 360 382+ 377 Specific Dispersion 106. 9 103. 7 106. 3 109. 5 107. 6 105. 1 107. 2 Approx. Composition, Per Cent Para 50 80 50 50 50 80 46 Aromatics; 10 5 10 12 10 12 Nzmhthenes 40 15 40 38 10 43 1 01' any out. o

The above results indicate that even in the 35 F. and a pressure over 100,000 lbs. per square absence of traces of promoter, high conversions, particularly of the olefin were obtained at 550 F. and 90 minutes reaction time. It is furthermore evident from these data that the process of this invention will yield products not obtainable in a simple aggregation of olefin polymerizing and high pressure cracking steps, but will produce new and useful results not hitherto recognized as obtainable.

The foregoing description "does not by any means cover the possible uses of our invention nor the'forms which it may assume, but serves to illustrate its fundamental principles and an assembly in which the novel features as disclosed above have been incorporated. It is obvious that changes in the details may-be made without departing from either its novel characteristics or the spirit and scope of our invention as defined in the appended claims.

The nature and objects of the present inven-' tion having been thus fully set forth and specific examples of the same given, what is claimed as new and useful and desired to be secured by inch.

2. Process for obtaining hydrocarbons of higher molecular weight by reacting propylene with isobutane which consists of subjecting a mixture of said hydrocarbons containing about 30 mol percent of propylene to a temperature of 550 to 650 F. and a pressure of 125,000 lbs. per square inch.

' FRANCIS R; RUSSELL.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,332,321 Korpi Oct. 19, 1943 2,349,211 Tulleners May 16, 1944 2,379,751 Russell July 3, 1945 2,396,217 Vaughan et a1 Mar. 5, 1946 2,407,033 OKelly et al Sept. 3, 1946 2,410,070 Horton Oct. 29, 1946 2,414,311 Larson Jan. 14, 1947 OTHER REFERENCES Chem. Eng. Handbook, 2nd ed. (McGraw-Hill), 1941, page 2183. 

1. PROCESS FOR OBTAINING HYDROCARBONS OF HIGHER-MOLECULAR WEIGHT BY REACTING OLEFINS WITH ISOPARAFFINS WHICH CONSISTS OF SUBJECTING A MIXTURE OF SAID HYDROCARBONS CONTAINING ABOUT 30 MOL PERCENT OF OLEFINS TO A TEMPERATURE ABOVE 300* F. AND A PRESSURE OVER 100,000 LBS. PER SQUARE INCH. 